Reactions of [Cp*Ru(H2O)(NBD)](+) with dihydrogen, silanes, olefins, alkynes, and allenes

Formal [2+2+2] addition reactions of the NBD ligand in [Cp*Ru(H2O)(NBD)]BF4 (NBD = norbornadiene) with H-2, Ph3SiH, ArCH=C=CH2, and RC=-CPh were observed. In contrast, olefins such as styrene and NBD do not undergo similar [2+2+2] addition reactions with [Cp*Ru(H2O)(NBD)]BF4. [Cp*Ru(H2O)(NBD)]BF4 reacts with H-2 in benzene to give [Cp*Ru(eta(6)-C6H6)]BF4 and nortricyclene. Similarly, [Cp*Ru(H2O)(NBD)]BF4 reacts with Ph3SiH to give [Cp*Ru(eta(6)-C6H5SiPh2OH)]BF4 and nortricyclene.

Reactions of Hydrotris(pyrazolyl)borate (Tp)-Supported Ruthenium Dihydrogen Complexes [TpRu(L2)(H2)]+ (L2 = dppm, dppp, (PPh3)2) with O2

The η2-dihydrogen complex [TpRu(L2)(H2)]+ (L2 = dppm, dppp, or (PPh3)2) prepared in situ by protonation of the hydride precursor reacts with O2 to yield the paramagnetic RuIII-superoxo complex [TpRuIII(L2)(O2)]+, in which antiferromagnetic coupling between the RuIII ion (d5, S = 1/2) and the coordinated superoxide radical (S = 1/2) does not seem to be present.